Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of propene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
  • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
  • H01M50/121—Organic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
  • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
  • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
  • H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/531—Electrode connections inside a battery casing
  • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/572—Means for preventing undesired use or discharge
  • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
  • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
  • H01M50/591—Covers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2314/00—Polymer mixtures characterised by way of preparation
  • C08L2314/06—Metallocene or single site catalysts
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/10—Homopolymers or copolymers of propene
  • C09J123/14—Copolymers of propene
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a resin composition, a film comprising the resin composition, and use thereof.
• polypropylenes have been widely used as thermoplastic forming materials having, for example, high rigidity, heat resistance, and transparency. Since these polypropylenes are nonpolar materials, they have poor adhesiveness to, for example, metallic materials such as aluminum and polar materials such as ethylene ⁇ vinyl alcohol copolymers. For the purpose of improving adhesiveness, techniques of modifying polypropylenes with an unsaturated carboxylic acid or a derivative thereof have been widely known. Moreover, since the polypropylene has poor flexibility, a soft rubber component is usually compounded into the polypropylene upon use as an adhesive resin. There is proposed a polypropylene-based adhesive resin in which adhesive properties have been improved by compounding a soft rubber component to polypropylene (Patent Literature 1).
• Patent Literature 2 proposes a multilayer film for drawing.
• polypropylenes are also used as a construction/industrial material because of, for example, their moderate flexibility, abrasion resistance, scratch resistance, heat resistance, chemical resistance, and post-processability.
• the construction/industrial material include, for example, decorative films that are used as decorative boards in which they are adhered on surfaces of wood boards, inorganic boards and metal plates, for example, with adhesives.
• Patent Literature 3 proposes a technology for bonding a patterned layer on a base film that constitutes a decorative film and a polypropylene protective layer for protecting the pattern layer via a polypropylene-based adhesive resin layer.
• metal cans have conventionally been used for secondary batteries, representative examples including lithium ion batteries.
• laminated packaging materials in which a composite of an aluminum foil stacked with a resin film was formed into a bag, have been used in response to demand for thinner and more diversified products.
• a metal lead base material made of, for example, aluminum or nickel is attached to metal base materials of positive and negative electrodes of lithium ion batteries in order to extract electricity.
• a film-shaped insulator (tab lead film) is generally interposed between the lead base material and the innermost resin layer (sealant) of the laminate packaging material and sealed at the sealing portion of the lead base material in order to improve a sealing strength therebetween.
• Patent Literatures 4 to 6 propose sealing materials for tab leads, such as tab lead films.
• films with adhesiveness have been required to improve adhesiveness at low temperatures, which enables bonding with less heat, in order to improve their productivity.
• films for a food packaging material which are processed into container shapes such as cups and trays and then used
• films for a construction/industrial material such as decorative films
• components for secondary batteries such as an exterior material for lithium ion batteries
• fabrication such as drawing and folding, which thereby requires prevention of whitening upon fabrication as well.
• conventional technologies such as those described in Patent Literatures 2 to 6 have been difficult to satisfy these requirements.
• the present invention was made in view of the aforementioned problems, and on abject of the present invention is to provide a food packaging material and a construction/industrial material, which are excellent in adhesiveness at low temperatures and prevention of whitening, an adhesive resin composition capable of forming a component for secondary batteries, a film containing the resin composition, a food packaging material and a construction/industrial material including the films, and a component for secondary batteries.
• the present inventors have made investigations to solve the aforementioned problems. As a result, the present inventors have found that the aforementioned problems can be solved by the following aspects, and thus have completed the present invention.
• a food packaging material and a construction/industrial material which are excellent in adhesiveness at low temperatures and prevention of whitening, an adhesive resin composition capable of forming a component for secondary batteries, a film containing the resin composition and a food packaging material and a construction/industrial material including the films, and a component for secondary batteries, can be provided.
• the resin composition of the present invention contains a propylene-based polymer (A) and a polyolefin (C) including structural units derived from an unsaturated carboxylic acid and/or a derivative thereof, and can further contain a propylene-based polymer (B) or an ethylene-based polymer (D), or a propylene-based polymer (B) and an ethylene-based polymer (D).
• Examples of the propylene-based polymer (A) include propylene homopolymers, or copolymers of propylene and at least one ⁇ -olefin having 2 to 20 carbon atoms excluding propylene.
• examples of the ⁇ -olefins having 2 to 20 carbon atoms excluding propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and preferred is ethylene or ⁇ -olefins having 4 to 10 carbon atoms.
• the copolymer of propylene and these ⁇ -olefins may be random copolymers, or may be block copolymers.
• the structural units derived from these ⁇ -olefins can be included in a proportion of 35 mol % or less and preferably 30 mol % or less in the copolymer of the ⁇ -olefins and propylene.
• the propylene-based polymer (A) satisfies the following requirement (a):
• the melting point (Tm) is preferably 100 to 115°C and more preferably 100 to 110°C.
• the propylene-based polymer (A) desirably has a melt flow rate (MFR) in a range of 0.01 to 1,000 g/10 minutes and preferably 0.1 to 100 g/10 minutes, as measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238.
• MFR melt flow rate
• the aforementioned propylene-based polymer (A) can have either an isotactic structure or syndiotactic structure, taking into consideration compatibility with the propylene-based polymer (B), as described below.
• examples of forms of the propylene-based polymer (A) include an isotactic propylene-based polymer (A1) and a syndiotactic propylene-based polymer (A2).
• Examples of the isotactic propylene-based polymer (A1) include a homopolypropylene excellent in heat resistance, for example, a known homopolypropylene that usually has 3 mol% or less of a copolymer component other than propylene, and a block polypropylene excellent in balance between heat resistance and flexibility, for example, a known block propylene that usually has 3 to 30% by mass of a n-decane-eluted rubber component, and a random polypropylene excellent in balance between flexibility and transparency, for example, a known random polypropylene, a melting peak of which is usually lower than 120°C and 100°C or higher and preferably in a range of 100 to 110°C, as measured by differential scanning calorimetry (DSC), and the isotactic propylene-based polymer (A1) can be appropriately selected from among these in order to obtain target physical properties, or two or more of the aforementioned polypropylene components with different melting points and rigidity can be combined for use.
• Such an isotactic propylene-based polymer (A1) can be produced, for example, through polymerization of propylene or copolymerization of propylene and other ⁇ -olefin, in a Ziegler catalyst system composed of solid catalyst components containing, for example, magnesium, titanium, halogen, and an electron donor as essential components, an organic aluminum compound, and an electron donor, or in a metallocene catalyst system using a metallocene compound as one component of the catalyst.
• the syndiotactic propylene-based polymer (A2) includes 90 mol% or more of a structural unit derived from propylene and 10 mol% or less of structural units derived from one or more selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms, and preferably 91 mol% or more of a structural unit derived from propylene and 9 mol% or less of structural units derived from one or more selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms, provided that the total of both structural units is 100 mol%.
• Examples of the ⁇ -olefins having 4 to 20 carbon atoms include, for example, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
• the syndiotactic propylene-based polymer (A2) usually has a melting peak of lower than 120°C and 100°C or higher and preferably in a range of 100 to 110°C, as measured by a differential scanning calorimeter DSC.
• the syndiotactic propylene-based polymer (A2) can be produced by a method described in WO2011/078054 , for example.
• the propylene-based polymer (B) satisfies the following requirement (b):
• the propylene-based polymer (B) has a MFR measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238 being in a range of 0.01 to 100 g/10 minutes, and satisfies requirements (b-1) and (b-2) below:
• the melt flow rate (MFR; ASTM D1238, 230°C, under 2.16 kg load) of the propylene-based polymer (B) is 0.01 to 100 g/10 minutes and preferably 0.1 to 30 g/10 minutes.
• the propylene-based polymer (B) also satisfies requirements (b-1) and (b-2).
• the melting point (Tm) as observed in differential scanning calorimetry is lower than 100°C, or no melting point is observed.
• no melting point is observed indicates that in differential scanning calorimetry, a crystal melting peak having an amount of heat upon crystal melting of 1 J/g or more is not observed in the range of -150 to 200°C.
• the details of the condition for the measurement of the melting point are as described in Examples later.
• the aforementioned melting point (Tm) is preferably 90°C or lower and more preferably 80°C or lower.
• the melting point (Tm) satisfying the aforementioned conditions, is preferable in terms of compatibility with a propylene-based polymer and adhesiveness at low temperatures.
• the propylene-based polymer (B) has a constituent unit derived from propylene and a constituent unit derived from at least one olefin selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms, and the content of the constituent unit derived from at least one ⁇ -olefin selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms is 40 mol% or less.
• Examples of the ⁇ -olefins having 4 to 20 carbon atoms include, for example, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
• the at least one olefin selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms is particularly preferably ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene.
• the content of the constituent unit derived from at least one ⁇ -olefin selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms is preferably 40 mol% or less and more preferably 35 mol% or less.
• the density of the propylene-based polymer (B) measured by JIS K7112 is preferably 0.85 to 0.89 g/cm 3 and more preferably 0.86 to 0.88 g/cm 3 .
• the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (B) measured in decalin at 135°C is desirably 0.1 to 10 dL/g and preferably 0.5 to 10 dL/g.
• This propylene-based polymer (B) has a single glass transition temperature, and the glass transition temperature (Tg) obtained by differential scanning calorimetry (DSC) is usually in a range of -50°C to 10°C, preferably -45°C to 5°C, and more preferably -40°C to 0°C.
• the propylene-based polymer (B) is excellent in cold resistance and lowered temperature properties when the glass transition temperature (Tg) is within the aforementioned range, which is preferred.
• Differential scanning calorimetry is performed as follows, for example.
• a sample of approximately 10.00 mg is packed in a dedicated aluminum pan, raised to a temperature from 30°C to 200°C at 200°C/min and held at 200°C for 5 minutes, and then it is lowered to a temperature from 200°C to -100°C at 10°C/min and held at -100°C for 5 minutes, then to determine a glass transition temperature (Tg) from an endothermic curve upon raising temperature at 10°C/minutes.
• Tg glass transition temperature
• a molecular weight distribution (Mw/Mn in terms of polystyrene, Mw: weight-average molecular weight, Mn: number-average molecular weight) of the propylene-based polymer (B) as measured by GPC is preferably 3.5 or less and more preferably 3.0 or less.
• the lower limit value is also 1.5 or more, for example.
• the propylene-based polymer (B) may be partially graft-modified by polar monomers.
• polar monomers include, for example, a hydroxyl group-containing ethylenically unsaturated compound, amino group-containing ethylenically unsaturated compound, epoxy group-containing ethylenically unsaturated compound, aromatic vinyl compound, vinyl ester compound, and vinyl chloride.
• the modified propylene-based polymer (B) is obtained by allowing the propylene-based polymer (B) as described above to be graft-polymerized with polar monomers.
• the polar monomer is usually used in an amount of 0.1 to 10 parts by mass and preferably 0.1 to 5 parts by mass, per 100 parts by mass of the propylene-based polymer (B).
• This graft polymerization is usually performed in the presence of a radical initiator.
• a radical initiator an organic peroxide or an azo compound, for example, can be used.
• the radical initiator can be mixed as is with the propylene-based polymer (B) and polar monomer and used, or can be dissolved in a small amount of organic solvent and then used. Any organic solvent that can dissolve the radical initiator can be used without limitation in particular.
• a reducing substance may be used. Use of the reducing substance can improve the graft amount of the polar monomer.
• Graft modification of the propylene-based polymer (B) with polar monomers can be carried out by conventionally known methods, and can be carried out by, for example, dissolving the propylene-based polymer (B) in an organic solvent, then adding a polar monomer and a radical initiator, for example, to the solution, and reacting the mixture at a temperature of 70 to 200°C and preferably 80 to 190°C, for 0.5 to 1.5 hrs, preferably 1 to 10 hours.
• a modified propylene polymer (B) can also be produced by reacting the propylene-based polymer (B) with a polar monomer without a solvent by using, for example, an extruder. This reaction is usually desirably carried out at a temperature of the melting point of the propylene-based polymer (B) or higher and specifically at 120 to 250°C, and usually for 0.5 to 10 minutes.
• the amount modified (amount grafted with a polar monomer) of the modified propylene-based polymer thus obtained is desirably usually 0.1 to 10% by mass, preferably 0.1 to 5% by mass, and more preferably 0.5 to 5% by mass.
• the propylene-based polymer composition of the present invention containing the aforementioned modified propylene-based polymer may result in rendering excellent adhesiveness and compatibility with other resins and improve wettability of a formed body surface.
• the propylene-based polymer (B) can be produced by employing, for example, the method as described in WO2004/087775 .
• Preferred forms of the propylene-based polymer (B) include the following propylene ⁇ 1-butene copolymer (B1), propylene ⁇ ethylene copolymer (B2), propylene ⁇ ethylene ⁇ 1-butene copolymer (B3), and atactic propylene homopolymer (B4).
• the aforementioned propylene ⁇ 1-butene copolymer (B1) includes a constituent unit derived from propylene in an amount of 60 to 90 mol% and preferably 70 to 85 mol%, in the aforementioned propylene-based polymer (B).
• the propylene ⁇ 1-butene copolymer (B1) having such a composition has favorable compatibility with the propylene polymer (A).
• the propylene ⁇ ethylene copolymer (B2) includes a constituent unit derived from propylene in an amount of 60 to 95 mol% and preferably 75 to 90 mol%, in the aforementioned propylene-based polymer (B).
• the propylene ⁇ ethylene ⁇ 1-butene copolymer (B3) includes a constituent unit derived from propylene in an amount of 60 to 95 mol% and preferably 70 to 90 mol%, and a constituent unit derived from ethylene in an amount of 2 to 25 mol% and preferably 5 to 20 mol%, and a constituent unit derived from 1-butene in an amount of 3 to 30 mol% and preferably 5 to 25 mol%, in the aforementioned propylene-based polymer (B).
• the atactic propylene homopolymer (B4) has a mesopentad fraction of 20 to 80% and preferably 30 to 60%, in the aforementioned propylene-based polymer (B).
• the polyolefin (C) is obtained by modification of a polyolefin with an unsaturated carboxylic acid and/or a derivative thereof, and contains structural units derived from the unsaturated carboxylic acid and/or the derivative thereof.
• Examples of the polyolefin to be modified can include a polypropylene (c1), ethylene ⁇ propylene ⁇ -olefin copolymer (c2), and ethylene ⁇ -olefin copolymer (c3).
• polyolefins (C) may be used singly or as a mixture of two or more thereof.
• the polyolefin (C) may be one of a modified product of the polypropylene (c1), modified product of the ethylene ⁇ propylene ⁇ -olefin copolymer (c2), and modified product of the ethylene ⁇ -olefin copolymer (c3), or may be a mixture of two or more thereof.
• the polypropylene (c1) may be a homopolymer of propylene and/or a propylene ⁇ -olefin copolymer, for example.
• the ⁇ -olefin preferably include, but are not limited to, ethylene and ⁇ -olefins having 4 to 20 carbon atoms, and these ⁇ -olefins may be used singly or in combinations of two or more thereof.
• Preferred ⁇ -olefin is ethylene and an ⁇ -olefin having 4 to 10 carbon atoms, and among these, particularly suitable are ethylene and an ⁇ -olefin having 4 to 8 carbon atoms.
• the content of a structural unit derived from propylene in the propylene ⁇ -olefin copolymer is at least 50 mol % or more and less than 100%.
• the polypropylene (c1) preferably has an intrinsic viscosity [ ⁇ ] of 0.1 to 10 dl/g.
• An intrinsic viscosity [ ⁇ ] in this range can yield a composition excellent in high formability and mechanical strength.
• Methods for producing the polypropylene (c1) are not particularly limited, and include well-known methods using well-known catalysts such as a Ziegler-Natta catalyst and metallocene catalyst.
• the polypropylene (c1) is preferably a crystalline polymer, and if the polypropylene (c1) is a copolymer, it may be a random copolymer or may be a block copolymer. Furthermore, the polypropylene (c1) may have any stereoregularity and any molecular weight without particular limitation as long as the (c1) satisfies its formability and has a sufficient strength in use when formed into a formed body. A commercially available resin can also be used as is.
• the ethylene ⁇ propylene ⁇ -olefin copolymer (c2) is specified by the following requirements (i) and (ii), for example: (i) The ethylene ⁇ propylene ⁇ -olefin copolymer (c2) contains 45 to 90 mol% of a structural unit derived from propylene, 2 to 25 mol% of a structural unit derived from ethylene, and 3 to 30 mol% of a structural unit derived from an ⁇ -olefin having 4 to 20 carbon atoms. (ii) The intrinsic viscosity [ ⁇ ] at 135°C in decalin is in a range of 0.1 to 10 dl/g.
• ⁇ -olefins having 4 to 10 carbon atoms can be suitably used and may be used singly or in combinations or two or more thereof.
• the proportions of structural units derived from propylene, ethylene, and the ⁇ -olefin are preferably 60 to 95 mol% for propylene, 2 to 25 mol% for ethylene, and 3 to 30% for the ⁇ -olefin, respectively, and further preferably 70 to 90 mol% for propylene, 5 to 20 mol% for ethylene, and 5 to 25 mol% for the ⁇ -olefin.
• the intrinsic viscosity [ ⁇ ] is in the range of more preferably 0.5 to 8 and further preferably 0.8 to 6.
• the intrinsic viscosity [ ⁇ ] in this range can yield an adhesive having an excellent balance between the flexibility and the mechanical strength and having a high adhesive strength.
• a method for producing the ethylene ⁇ propylene ⁇ -olefin copolymer (c2) is not particularly limited, and can be produced by well-known methods using well-known catalysts such as a Ziegler-Natta catalyst and metallocene catalyst.
• the ethylene ⁇ propylene ⁇ -olefin copolymer (c2) may have any stereoregularity and any molecular weight without particular limitation as long as the (c2) satisfies its formability and has a sufficient strength in use when formed into a formed body.
• a commercially available resin can also be used as is.
• the ethylene ⁇ -olefin copolymer (c3) is specified by the following requirements (iii) and (iv):
• ⁇ -Olefins having 3 to 10 carbon atoms are more suitable, and one type thereof may be used singly or two or more types thereof may be used.
• the proportions of structural units derived from each monomer are preferably 55 to 98 mol% for ethylene and 2 to 45 mol% for the ⁇ -olefin, respectively, and more preferably 60 to 95 mol% and 5 to 40 mol%, respectively.
• the intrinsic viscosity [ ⁇ ] is in the range of more preferably 0.5 to 8 and further preferably, 0.8 to 6.
• the intrinsic viscosity [ ⁇ ] in this range can yield a composition having an excellent balance between the flexibility and the mechanical strength and having a high adhesive strength.
• Examples of methods for producing the ethylene ⁇ -olefin copolymer (c3) include, but should not be particularly limited to, a well-known method in the presence of a well-known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
• a well-known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
• the molecular weight of the ethylene ⁇ -olefin copolymer (c3) is also not particularly limited as long as it has excellent formability and a strength enough to withstand use when formed into a formed body.
• a commercially available resin can also be used as is for the ethylene ⁇ -olefin copolymer (c3).
• Examples of the unsaturated carboxylic acids and/or derivatives thereof used for modification of these polyolefins can include unsaturated compounds having one or more carboxylic groups, esters of compounds having a carboxylic group and alkyl alcohols, and unsaturated compounds having one or more anhydrous carboxylic group, for example.
• Examples of the unsaturated groups included in the unsaturated compounds can include a vinyl group, vinylene group, and unsaturated cyclic hydrocarbon group, for example.
• These unsaturated carboxylic acids and/or derivatives thereof can be used singly or in combinations of two or more thereof.
• suitable are unsaturated dicarboxylic acids or acid anhydrides thereof, and particularly preferred are maleic acid, nadic acid, or acid anhydrides thereof.
• the amount of structural units derived from the unsaturated carboxylic acid and/or the derivative thereof contained in the polyolefin (C) is preferably 0.01 to 10% by mass in terms of structural unit derived from maleic anhydride and more preferably 0.1 to 5% by mass.
• the amount of structural units derived from the unsaturated carboxylic acid and/or the derivative thereof in this range can yield a resin composition having an excellent balance between the formability and the adhesiveness.
• a content proportion of a structural unit derived from propylene in structural units excluding the structural units derived from the aforementioned unsaturated carboxylic acid and/or the derivative thereof is preferably 80 to 100 mol% and more preferably 90 to 100 mol%.
• the content proportion of the structural unit derived from propylene in this range can yield a resin composition excellent in heat resistance.
• Methods for allowing grafting of the unsaturated carboxylic acid and/or its derivative are not particularly limited, and can employ any conventionally known graft polymerization methods such as a solution method and melt kneading method. Examples thereof include, for example, a method for melting a polyolefin, thereto adding the unsaturated carboxylic acid and/or its derivative thereof to carry out a graft reaction; or a method for dissolving a polyolefin in a solvent to prepare solution, and adding the unsaturated carboxylic acid and/or the derivative thereof to carry out a graft reaction.
• the ethylene-based polymer (D) satisfies the following requirement (d): (d)
• the ethylene-based polymer (D) is an ethylene homopolymer or a copolymer of ethylene and at least one ⁇ -olefin selected from ⁇ -olefins having 3 to 20 carbon atoms, and has a MFR of 0.1 to 10 g/10 minutes as measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238.
• the MFR is preferably in a range of 0.1 to 8 g/10 minutes and further preferably in the range of 0.1 to 6 g/10 minutes. Within the aforementioned range of MFR, a composition with excellent balance between flexibility and mechanical strength and a high adhesive strength, can be yielded.
• the aforementioned copolymer is preferably an ethylene ⁇ -olefin copolymer containing 50 to 99 mol% of a constituent unit derived from ethylene and 1 to 50 mol% of a constituent unit derived from an ⁇ -olefin selected from ⁇ -olefins having 3 to 20 carbon atoms.
• the aforementioned copolymer that is an ⁇ -olefin having 3 to 10 carbon atoms is more suitably used as the ⁇ -olefin, and one type of ⁇ -olefin may be used singly or two or more types thereof may be used as long as they are in this range.
• the ratio of ethylene: 55 to 98 mol% and the ratio of ⁇ -olefin: 2 to 45 mol% are preferred, and further preferred are the ratio of ethylene: 60 to 95 mol% and the ratio of ⁇ -olefin: 5 to 40 mol%.
• the ethylene-based polymer (D) can be produced by a well-known method such as a high pressure method or a method in the presence of a well-known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst, however, the method is not be particularly limited thereto. Furthermore, the molecular weight is also not particularly limited as long as the ethylene-based polymer (D) satisfies formability and has a sufficient strength in use when formed into a formed body. A commercially available resin can also be used as is.
• the ethylene-based polymer (D) may be grafted with a small amount of, for example, maleic anhydride as long as it satisfies the aforementioned conditions. Moreover, a small amount of, for example, maleic anhydride is grafted, and the grafted monomer is then further modified with, for example, a diamine or carbodiimide as long as the aforementioned conditions are satisfied.
• other components such as a propylene ⁇ ethylene block copolymer, which is different in composition from the present invention, propylene homopolymer, propylene ⁇ ethylene random copolymer, propylene ⁇ 1-butene random copolymer, propylene ethylene ⁇ 1-butene random copolymer, styrenic elastomer, and polyethylene, may be appropriately included to the extent that the effects of the invention are not impaired.
• the proportions of the other components in the resin composition according to the present invention are preferably 20% by mass or less.
• the resin composition according to the present invention may contain known additives such as antioxidants, ultraviolet absorbing agents, neutralizers, nucleating agents, light stabilizers, antistatic agents, anti-blocking agents, lubricants, odor adsorbents, antibacterial agents, pigments, inorganic and organic fillers, and a variety of synthetic resins as necessary.
• additives such as antioxidants, ultraviolet absorbing agents, neutralizers, nucleating agents, light stabilizers, antistatic agents, anti-blocking agents, lubricants, odor adsorbents, antibacterial agents, pigments, inorganic and organic fillers, and a variety of synthetic resins as necessary.
• the resin composition according to the present invention can be produced by a known conventional method.
• the components described above can be melt kneaded to produce the resin composition.
• the contents of the propylene-based polymer (A), propylene-based polymer (B), polyolefin (C), and ethylene-based polymer (D) in the resin composition of the present invention per 100 parts by mass of the total content of the propylene-based polymer (A), propylene-based polymer (B), polyolefin (C), and ethylene-based polymer (D) are 10 to 99.9 parts by mass of propylene-based polymer (A), 0 to 40 parts by mass of propylene-based polymer (B), 0.1 to 20 parts by mass of polyolefin (C), and 0 to 40 parts by mass of ethylene-based polymer (D),
• the propylene-based polymer (A) is 10 to 94.9 parts by mass
• the propylene-based polymer (B) is 0 to 40 parts by mass
• the polyolefin (C) is 0.1 to 20 parts by mass
• the ethylene-based polymer (D) is 5 to 40 parts by mass
• a more preferred aspect of the density of the ethylene-based polymer (D) is that it is 0.87 g/cm 3 or less.
• the density of the ethylene-based polymer (D) is 0.87 g/cm 3 or less
• the density is further preferably 0.80 g/cm 3 or more.
• the adhesiveness in particular adhesiveness under low heat, specifically at 140°C or lower, is high, and a film containing the layer obtained from the present composition is less likely to whiten upon deformation processing.
• the resin composition of the present invention preferably has a MFR of 0.1 g/10 minutes to 30 g/10 minutes and more preferably 1 g/10 minutes to 20 g/10 minutes, as measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238.
• MFR 0.1 g/10 minutes to 30 g/10 minutes and more preferably 1 g/10 minutes to 20 g/10 minutes, as measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238.
• resin compositions applicable to various film forming processing methods such as casting, inflation, and extrusion lamination methods, can be obtained.
• orientation of molecular chains is apt to be relaxed, which can inhibit whitening upon subsequent deformation processing.
• the fine cracks generated in a film are considered to lower insulation properties when the film is formed into a battery packaging material.
• the monolayer film and the multilayer film according to the present invention are monolayer films or multilayer films including at least one layer containing the resin composition.
• the monolayer film according to the present invention is a film composed of a layer containing the resin composition
• the multilayer film is a multilayer film including at least one layer containing the resin composition.
• the monolayer film and the multilayer film according to the present invention have excellent resistance to whitening upon deformation processing. Therefore, when the monolayer and multilayer film of the present invention are used as a food packaging material, a construction/industrial material, and a component for secondary batteries such as a component for lithium ion batteries, whitening is unlikely to occur upon fabrication of the films, such as drawing and folding. Therefore, the monolayer and multilayer film of the present invention can be suitably used as a food packaging material, a construction/industrial material, and a component for secondary batteries.
• polypropylene-based resins have been conventionally used as packaging materials that form exterior bodies of lithium ion batteries, however, the present invention has realized prevention of whitening which could not be avoided with conventional polypropylene-based resins, by using a specific combination of the aforementioned propylene-based polymer (A), propylene-based polymer (B), polyolefin (C) and ethylene-based polymer (D).
• the multilayer film of the present invention includes at least one layer containing the resin composition, and one or both sides of the layer containing the composition are in contact with further layers included in the multilayer film.
• the further layers in contact with the layer containing the composition include, for example, a metal-containing layer, polyolefin layer, and polar resin layer.
• the metal-containing layer can include, for example, an aluminum layer, copper layer, and stainless steel layer
• examples of the polyolefin layer can include, for example, a polypropylene layer, poly4-methylpentene layer, and polyethylene layer
• examples of the polar resin layer can include, for example, a polyamide layer, EVOH layer, PET layer, and PBT layer.
• the monolayer film and the multilayer film according to the present invention can be prepared through melt extrusion forming, and can be generally produced by methods industrially used, such as casting, inflation, or extrusion lamination methods.
• components for secondary batteries that are applications of the film of the present invention include, for example, a tab lead film for lithium ion batteries (hereinafter simply referred to as “tab lead film”) and an exterior material for lithium ion batteries (hereinafter simply referred to as “exterior material”).
• the tab lead is a terminal that conducts electricity in and out of electrodes in a battery, and has a metal layer as a lead base material and a tab lead film formed on at least one side of the lead base material.
• a layer (film) composed of the composition of the present invention is in contact with a lead base material and can have a further layer as necessary.
• the tab lead film partially covers the lead base material (lead conductor) and is formed in order to adhere to an inner surface of an exterior material in a lithium ion battery.
• the tab lead film of the present invention has excellent adhesiveness at low temperatures, which thereby enables adhesion temperature with the lead base material to be lowered than before, resulting in that a heat load upon adhesion can be reduced and its productivity can be improved.
• the adhesion temperature with the lead base material is not particularly limited as long as it is temperature at which the tab lead film melts, but is preferably 100 to 200°C and more preferably 130°C to 180°C.
• the heating time is also not particularly limited, but is preferably 1 second to 10 minutes and more preferably 1 second to 1 minute.
• One embodiment of the tab lead film of the present invention includes a stacked film having an adhesive layer composed of the composition of the present invention and a heat resistant layer.
• the adhesive layer is adhered to a lead base material, and the heat resistant layer is adhered to an inner surface of an exterior material.
• a lead base material connected to a positive electrode of a lithium ion battery for example, a lead conductor composed of aluminum, titanium, and an alloy containing at least one type selected therefrom is used.
• a lead base material connected to a negative electrode of a lithium ion battery for example, a lead conductor composed of copper, nickel, and an alloy containing at least one type selected therefrom is used.
• the heat resistant layer examples include, for example, a layer composed of a polyolefin resin.
• polyolefin resins include, for example, thermoplastic polyolefin resins such as polyethylene and polypropylene. These may be used in one type singly or two or more types thereof may be used.
• the polypropylene resin used is preferred in terms of heat resistance.
• the polyolefin resins may also be crosslinked.
• An aspect of the exterior material of the present invention is not particularly limited as long as it has an adhesive layer composed of the composition of the present invention and includes, for example, a laminate film having a configuration of a base material layer/aluminum foil layer/adhesive layer/sealant layer.
• the MFR of propylene-based polymer was measured at 230°C under a load of 2.16 kg, and the MFR of an ethylene-based polymer was measured at 190°C under a load of 2.16 kg, in accordance with ASTM D1238.
• the density was measured according to JIS K7112 (density gradient tube method).
• the content ratio of constituent units derived from an ⁇ -olefin and constituent units derived from ethylene, in a polyolefin was quantified by 13 C-NMR using the following apparatus and conditions.
• the melting point was measured using a differential scanning calorimeter (DSC) as follows. Approximately 5 mg of sample was sealed in an aluminum pan, heated from room temperature to 230°C at 10°C/min., and the sample was held at 230°C for 10 minutes for complete melting. The sample was then cooled to -20°C at 10°C/min, placed at -20°C for 10 minutes, and then heated again to 230°C at 10°C/min. The peak temperature in this second heating test was adopted as a melting point (Tm).
• DSC differential scanning calorimeter
• the amount of structural units derived from the unsaturated carboxylic acid and/or its derivative was determined by measuring an intensity of the peak derived from the aforementioned structural unit (1790 cm -1 when maleic anhydride was used) using an infrared absorption spectrometer and using a calibration curve preliminarily prepared.
• a JIS K6251 No. 2 dumbbell was punched out from the resulting monolayer film so that it was parallel to a flow direction of the monolayer film, and the hue L value was measured by a positive reflection light removal method on a spectrophotometer CM-3700A manufactured by Konica Minolta, Inc. Furthermore, the hue L value of the JIS K6251 No. 2 dumbbell that was subjected to elongation and deformation on a tensile tester by 5 mm, 10 mm, or 20 mm at a crosshead rate of 200 mm/min. The amount of change in hue L value after 5 mm elongation was ⁇ L (5 mm), that after 10 mm elongation was ⁇ L (10 mm), and that after 20 mm elongation was ⁇ L (20 mm).
• Each monolayer film was formed under three conditions of take-up rates of 5 m/min, 10 m/min, and 20 m/min.
• the monolayer films obtained under each condition were evaluated for film formability according to the following criteria: Formability O: No peel marks were observed on the film surface when the film passed through the cooling rolls. Formability ⁇ : Peel marks were slightly observed on the film surface when the film passed through the cooling rolls. Formability X: Peel marks were significantly observed on the film surface when the film passed through the cooling rolls.
• the extruded adhesive and polypropylene were stacked in the feed block so that the adhesive was an inner layer and the polypropylene was an outer layer to fabricate a 100 ⁇ m thick multilayer film with both the inner layer and outer layer being 50 pm.
• the inner layer of the resulting multilayer film and an aluminum foil layer of a commercially available aluminum laminate film were overlaid and heat-sealed by using a heat sealer at a sealing temperature of 120°C, 130°C or 140°C, sealing pressure of 0.1 MPa and a sealing time of 10 seconds, then to fabricate a composite.
• the adhesive strength (unit: N/15 mm) of the composite obtained at each sealing temperature was measured at room temperature of 23°C by a T-peel method using a tensile tester.
• the crosshead speed was 300 mm/min.
• Polyolefins used in Examples and Comparative Examples will be listed below. Note, however, all of these polyolefins were prepared by polymerization according to the ordinary method, unless otherwise specified.
• a resin composition was obtained by melting and kneading 80 parts by mass of PP-1, 10 parts by mass of EPR, and 10 parts by mass of modified PP at 230°C by using a single screw extruder. This composition was defined as Adhesive 1.
• Table 1 shows the MFR and density of each adhesive obtained in Examples and Comparative Examples, the results of resistance to whitening and formability evaluation of the monolayer film obtained from each adhesive, as well as the results of adhesive strength evaluation of the multilayer film obtained from each adhesive. Note, however, the adhesive strength of Adhesive 9 was not measured because the film caused a rough surface due to peel marks upon fabrication of the multilayer film.
• O O O O Take up speed 10 m/min.
• O O O ⁇ Take up speed 20 m/min.

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• 2022
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